Synthetic detergent composition



2,721,847 Patented Oct. 25, 1955 2,721,847 SYNTHETIC DETERGENT COMPOSITION Arthur Ira Gebhart, Union, N. J., and Irving Joseph Krems, Bronx, N. Y., assignors to Colgate-Palmolive Company, Jersey City, N. J., a corporation of Delaware No Drawing. Application March 28, 1950, Serial No. 152,522

20 Claims. (Cl. 252-152) The present invention relates to new synthetic detergent compositions, and, more particularly, to compositions of the type of the anionic sulfated and sulfonated detergents having improved properties, and to a process of preparing same.

There has been a considerable amount of research to discover substances or additives which aid the efliciency of detergent compositions. The problem is exceedingly complex, however, in view of the various physico-chemical mechanisms or properties and the like involved in the action of a detergent composition including suspension, colloid adsorption, interfacial tension, micellar structure, dispersion, foam stability, etc., and the general difiiculty usually in determining the particular mechanism which is being altered by modifications in the formulation of the detergent composition. In view of the varied nature of many synthetic detergents, moreover, additives in general exhibit a certain degree of specificity of action.

It has now been discovered that the incorporation of minor proportions of certain higher alkyl mononuclear aryl sulfonamide compounds in anionic sulfated and sulfonated detergents are effective to achieve a significant and synergistic enchancement in detergency, in addition to maintenance of a high level of foaming properties. These improvements are unique since the aromatic sulfonamide additives described herein by themselves have neither foaming nor deterging properties, and thus are valueless as cleansing agents per se.

The enhancing additives of the present invention are characterized by their essentially weakly polar nature, general limited water solubility, and by the presence of a higher alkyl substituted mononuclear aryl structure, a sulfonamide function, and a N-aliphatic weakly hydrophilic chain. More particularly, these additives may be represented by the formula:

where R is a higher alkyl group, having generally at least about 10 and preferably about 10 to 22 carbon atoms, X is a mononuclear aromatic radical, Y is selected from the class consisting of hydroxyalkyl chains, having preferably up to about 5 carbon atoms, and lower alkyleneoxy chains, and Z is selected from the class consisting of hydrogen, lower alkyl having preferably up to about 5 carbon atoms, and the groups specified for Y above, said alkyleneoxy chains having a total of not substantially in excess of about 9 molecular quantities of lower alkylene oxide.

The higher alkyl substituent on the aromatic nucleus may be branched or straight-chain in structure; it comprises moreover such groups as decyl, dodecyl, keryl, pentadecyl, hexadecyl, mixed long-chain alkyls derived from long-chain fatty materials, cracked parafiin wax olefins, polymers of lower mono-olefins, etc. It is preferred that the alkyl substituent averages about 12 to about 18 carbon atoms. For example, propylene may be polymerized to the tetramer and condensed with benzene in the presence of a Friedel-Crafts catalyst to yield essentially the dodecyl benzene derivative which is suitable for preparation of the desired sulfonamide type compounds. The aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, etc.

Included within the ambit of the invention are the following preferred classes of compounds suitable as additives and which may be represented by the structural formulas:

E-x-som wherein R and X have the significance set forth above, Y is a member of the class consisting of hydrogen and lower alkyl and Z is a lower hydroxyalkyl group, preferably containing up to about 5 carbon atoms. The hydroxyalkyl group may be monoor poly-hydroxyalkyl. Examples of suitable compounds are dodecyl benzene sulfonamido methanol, dodecyl benzene sulfonamido ethanol, keryl benzene sulfonamido-ethanol, dodecyl benzene N- ethyl sulfonamido-ethanol, dodecyl toluene sulfonamido propanol, dodecyl benzene sulfonamido butanol, dodecyl phenol sulfonamido ethanol, dodecyl benzene N-glyceryl sulfonamide, pentadecyl benzene N-glycol sulfonamide wherein the pentadecyl group is derived from a propylene pentamer, etc.

R-X-S O 2N wherein R and X are as described above, and Y and Z may be the same or different, each being a lower hydroxyalkyl group of preferably up to about 5 carbon atoms, and, more particularly, from about 2 to 5 each. The hydroxyalkyl group may similarly be monoor polyhydroxyalkyl. As exemplary of this class are dodecyl benzene N-diethanol sulfonamide, keryl benzene N-diethanol sulfonamide, pentadecyl benzene N-dipropanol sulfonamide, dodecyl benzene N-diisopropanol sulfonamide, dodecyl benzene N-dibutanol sulfonamide, dodecyl benzene N-di-glycol sulfonamide, etc.

3. The lower alkylene oxide addition products of the higher alkyl mononuclear aryl sulfonamides, and N-alkyl and N-alkylol (monoand di-N substituted) sulfonamicles having a reactive hydrogen atom. Using ethylene oxide with a N-methyl sulfonamide compound as an example, the following class of compounds may be formed:

wherein R and X are as previously described, and n is a small whole number from about 1 to not substantially in excess of about 9. As indicated, in place of the N- methyl sulfonamide, any suitable sulfonamide type compound may be used as a reactant. It is preferred to use the unsubstituted primary sulfonamide, the secondary mono-substituted N-alkyl or the monoor di-substituted N-hydroxyalkyl compounds, preferably wherein the N- substituent chains have up to about 5 carbon atoms such as described in classes 1 and 2 supra. Suitable examples are the ethylene oxide addition products of dodecyl benzene sulfonamide wherein 2,3,6 and 9 ethylene oxide groups have been introduced into the molecule. Instead of ethylene oxide, equivalent alkylene oxides such as propylene oxide and butylene oxide may be employed in the same manner.

The sulfonamide type additives of the present invention may be prepared in any suitable manner, with a few preferred modes of synthesis described below. The appropriate higher alkyl aryl compounds .or their sulfonic acid derivatives may be used as suitable starting materials. Using the alkyl aryl compouds as initial reactants, the suitable sulfonic acid derivatives may be formed by any convenient sulfonation procedure, e. g. reaction with oleum or chlorosulfonic acid.

The alkyl aryl sulfonamides containing hydroxyalkyl groups (e. g. classes 1-2 supra) may be prepared by condensation in a non-acidic medium of the appropriate alkyl aryl sulfonic acid derivatives, e. g. sulfonyl chloride, with suitable amino compounds generally. Thus, the sulfonyl chloride may be condensed, under Schotten- Baumann reaction conditions, with amines such as monoand di-ethanolamine to produce the corresponding N-ethanol and N-diethanol sulfonamides respectively, etc. A N-methylol derivative may be formed by the reaction of formaldehyde upon the sulfonamide having a suitable reactive hydrogen atom. The alkylene oxide addition products may be prepared by the reaction of the corresponding higher unsubstituted alkyl aromatic sulfonamides (prepared by the action of ammonia on the sulfonyl chloride similarly), and their N-alkyl and N-alkanol sulfonamide derivatives having at least one reactive hydrogen atom, with the appropriate lower alkylene X- ide. The alkylene oxide in gaseous form may be passed into the reaction mixture at elevated temperatures, e. g. 150250 C., to produce reaction products having a desired number of alkylene oxide groupings in the final product.

The novel compositions of the present invention contain as the active ingredient the anionic sulfated and sulfonated detergent, including suitable mixtures thereof.

lncluded therein are the aliphatic sulfated or sulfonated agents, such as the aliphatic acyl-containing compounds wherein the aliphatic acyl radical has about 8 to about 22 carbon atoms and, more particularly, the aliphatic carboxylic ester type having such an aliphatic acyl radical and containing at least about 10 and preferably about 12 to about 26 carbon atoms to the molecule. Among the aliphatic detersive compounds, it is preferred to use the sulfated aliphatic compounds having about 12 to about 22 carbon atoms. As suitable examples of aliphatic detergents may be found the sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, e. g. coconut oil monoglyceride monosulfate, tallow di-glyceride monosulfate; the long chain pure or mixed higher alkyl sulfates, e. g. lauryl sulfate, cetyl sul fate, higher fatty alcohol sulfates derived from coconut oil; the hydroxy sulfonated higher fatty acid esters, e. g. higher fatty acid esters of 2,3 di-hydroxy propane sulfonic acid; the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e. g. oleic acid ester of isethionic acid; the higher fatty acid ethanolamide sulfates; the higher fatty acid amides of amino alkyl sulfonic acids, e. g. lauric amide of taurine, and the like.

It is a particular feature of this invention that the effects are particularly enhanced with the alkyl aryl sulfonate detergents. These aromatic sulfonate detergents are also known in the art. They may be mononuclear or polynuclear in structure. More particularly the aromatic nucleus may be derived from benzene, toluene, xylene, phenol, cresols, naphthalene, derivatives of phenanthrene nuclei, etc. The alkyl substituent on the aromatic nucleus may vary widely, as long as the desired detergent power of the active ingredient is preserved. While the number of sulfonic acid groups present on the nucleus may vary it is usual to have one such group present in order to preserve as much as possible a balance between the hydrophilic and hydrophobic portions of the molecule.

More specific examples of suitable alkyl aromatic sulfonate detergents are the propylated naphthalene sulfonates, the mixed butyl naphthalene sulfonates, tetrahydronaphthalene sulfonates, the various butylated diphenyl sulfonates, and phenyl-phenol sulfonates. It is preferred, however, to use the higher alkyl aromatic sulfonates rather than the lower alkyl substituted detergents. Typical examples of this preferred class are the higher alkyl mononuclear aryl sulfonates wherein the alkyl group is about 10 to about 22, and preferably about 12 to 18 carbon atoms. Both the structure of the higher alkyl substituent and the monocyclic nucleus may vary in the manner described upon for such groups in the sulfonamide additives. More particularly, it is preferred to use the higher alkyl benzene sulfonates wherein the higher alkyl group is about 12 to 16 carbon atoms.

These various anionic detergents are commonly used in the form of their water soluble salts. Of these, the alkali metal (e. g. sodium, potassium, lithium) and ammonium salts are preferred though other salts such as the amine, alkylolamine, and alkaline earth metal (e. g. calcium, magnesium) salts may be used if desired. Their concentration in the detergent compositions of the present invention is generally at least about 10% by weight of the composition. Compositions with very high concentrations of these anionic detergents are prepared for specialized uses generally. With built compositions, however, it is preferred to use an anionic detergent content of about to 50% concentration. In liquid detergent compositions, any suitable concentration of anionic detergent may be employed, e. g. 90% of total solids content or -60% of the weight of the total liquid detergent composition.

The amount of sulfonamide additives in the detergent composition is less than the weight of the anionic detergent and is generally minor in proportion to the weight of the anionic detergent and effective in producing the desired improvements in detersive capacity. Generally, the proportion of sulfonamide additives should be from about 5 to about 50% of the weight of the anionic de tergent and will preferably be from about 1 to about 15% by weight of the detergent composition. Particularly effective results have been achieved wherein the additives are present in amounts of the order of about 5 to 10% of the total detergent composition.

The additives may be incorporated with the anionic detergent at any point during the manufacturing process at which subsequent operations will not adversely modify the properties of the detergent compositions. A variety of procedures which have proved to be convenient, economical, and productive of best results are: the additives may be added to a hot aqueous slurry of about to concentration of the active ingredient with vigorous stirring to form a smooth, uniform and homogeneous paste, the additives may be dissolved in a suitable solvent and added to the slurry of the anionic detergent, or a mixture or emulsion of the additives in water with a minor proportion of the active ingredient may be incorporated into the slurry.

Thereafter, these compositions may be prepared in the form of solutions, pastes or as dry or partially hydrated solid products, preferably in a finely divided condition. It is preferred to prepare the products in particulate form. Accordingly, the slurry of the detergent composition may be subjected to any suitable drying operations and converted to particle form. The mixture may thus be subjected to conventional spray-drying, roll drying or drum drying operations utilizing temperatures above about 212 F. to obtain the desired detergent particles.

It is common to employ various adjuvant materials in synthetic detergent compositions. The detergent compositions of the present invention may include any of these substances employed by the art in admixture with such detergent compositions generally, provided the use of any such materials does not completely neutralize or remove the effect of the sulfonamide type additives in the relationship set forth. These adjuvant builders or additives may be inorganic or organic in structure and may be mixed with the active ingredient in any suitable manner. Such conventional inorganic builders or additives as the various alkali metal phosphates (e. g. tri-polyphosphate, hexametaphosphate, tetrapyrophosphate) the alkali metal silicates, sulfates, carbonates, etc. may be employed in these compositions. Suitable organic materials such as sodium carboxymethylcellulose may also be employed herein. It is preferred that the detersive compositions in particulate form contain major amounts of alkaline builders, particularly the inorganic water soluble phosphates. The total amount of phosphate compounds should be a minimum of at least about and preferably from about 10 to about 60% by weight of the detergent composition for best results. An amount of active ingredient of about to 50% with the requisite minor proportion of sulfonamide type additives and about to about 60% total phosphate compounds exhibits particularly desirable properties for a detergent composition. For use as liquid detergents, the active ingredient should be in the form of a highly water soluble salt, e. g. ammonium, mono, diand triethanol ammonium salts, and the detergent composition may be prepared in dilute or concentrated aqueous solution with or without the presence of a lower molecular weight aliphatic alcohol such as ethyl alcohol, propylene glycol, etc. An amount of anionic detergent of about 20 to 60%, and preferably about 40 to 60%, by weight of the total liquid detergent composition and an effective minor proportion of the sulfonamide type additive, the remainder of the composition consisting essentially of a diluent, exhibits also highly improved results.

The eifect on detergency of compositions of the present invention may be indicated by a standard soil removal test. This testing procedure involves the uniform soiling, washing with particular detergent compositions at 110 F.:2 F., and drying of a large number of cotton swatches. The whiteness of the various test swatches are measured by a Hunter reflectometer. The units of soil removed may be calculated by subtracting the average reflectivity of unwashed control samples from the washed swatches. 7

Table I indicates the percent change in soil removal on cotton swatches using a standard detergent composition consisting essentially of 35% sodium salts of dodecyl benzene sulfonate (the dodecyl group being derived from a propylene tetramer), 40% sodium tri-polyphosphate, and sodium sulfate, with and Without the dodecyl benzene sulfonamide type additive, at 0.75% total concentration in distilled water. The percentages listed in the table for each additive at 2%, 5% and 10% addition by Weight to the standard detergent composition represent the percent change in soil removal using as a standard the above detergent composition without organic additive. A value indicates improved soil removal and a value represents decreased soil removal, in comparison to the standard.

TABLE I Percent change in soil removal on cotton soil The marked improvement in soil removal due to the presence of the alkyl aryl sulfonamide type additives of the present invention is evident from the data It. is apparent that the sulfonethanolamides, and the lower ethylene oxide addition products give consistent improvement in soil removal using varying percentages of additives. length there are produced derivatives which do not produce any apparent beneficial effects, and may even inhibit soil removal in the relationship set forth. Thus, improvement in soil removal may be effected with sulfonamide additives of up to about 9 mols ethylene oxide by use of the proper proportions of additive, which may be determined by routine tests. The higher ethylene oxide addition products, e. g. 14.5 mols ethylene oxide and above, appear to have an adverse effect upon detergency under the indicated testing conditions. Thus, sulfonamide addition products with 18.2 mols, 25.2 mols, 37.1 mols and 53.8 mols of ethylene oxide have an adverse eifect on soil removal similar to the undesirable results achieved with the 14.5 mols ethylene oxide addition product disclosed in Table I.

For each specific sulfonamide type additive there is an optimum proportion or concentration which may be determined by routine tests. Referring to Table I, the sulfonmonoethanolamide additive appears to exert its optimum effect in the specific detergent compositions and under the conditions set forth at about 2% concentration, whereas the sulfondiethanolamide exerts optimum efiect at about 10% in the same relationship.

The sulfonamide additives of the present invention achieve an even more remarkable and significant improvement in soil removal on woolen fabrics, in comparison to the desirable effects achieved on cotton soil as disclosed supra. Using substantially the same testing conditions with the identical detergent compositions, the percent change in soil removal on wool soil is set forth in Table II:

The synergistic improvements resulting from the use of the organic additives described above are graphically evident from the data. The results with the di-ethanol deratives and the like are in general highly superior to the ethylene oxide derivatives.

1 Another important feature is that the sulfonamide type additives referred to herein have been observed to have in general relatively little or no deleterious action on the initial volume or stability of foam of alkyl aryl sulfonate washing compositions. Such results are particularly important since it is desirable that the detergent compositions exhibit excellent foaming properties, particularly for consumer appeal and certain home and industrial uses. Many of the hitherto known organic additives have a pronounced adverse effect on foaming properties, particularly foam stability, whereas the novel compositions of the present invention exhibit marked foam stability.

Another feature of the present invention is that the improved results may be exhibited both in hard and in soft water, and over a wide range of washing concentrations. While additives may in general exert widely variable effects in hard water from those achieved in soft water the novel compositions of the present invention are generally remarkably effective in both types, thereby enlarging their field of application to a great degree. The wide range of suitable washing conditions under which the improved results are obtained is significant also since it' permits economy of use and allows a wide latitude to the As the ethylene oxide chain increases in consumer and the like as to suitable quantities to be employed.

The following examples are additionally illustrative of the nature of the present invention and it will be understood that the invention is not limited thereto:

EXAMPLE I A detergent composition is prepared by forming about a 60% solids slurry containing on a solids basis about 35% sodium propylene tetramer benzene sulfonate salt, 40% tri-polyphosphate, 15% sodium sulfate, propylene tetramer benzene sulfondiethanolamide, and the remainder minor amounts of sodium chloride, sodium hydroxide, sodium carboxymethylcellulose, etc. This slurry is agitated at about 140 F. in a conventional soap crutcher to form a homogeneous composition. The slurry is submitted to spray-drying with air at a temperature of about 350 F. with a resultant moisture loss of about 40%. The resulting composition is recovered in the form of homogeneous beads, and possesses a high degree of detersive properties in both hard and soft water.

EXAMPLE II The procedure of Example I is repeated with the modifications that the active ingredient consists essentially of the keryl benzene sulfonate salt, the organic additive is the addition product of keryl benzene sulfonamide with 3 mols of ethylene oxide, and the slurry is roll dried at about 50 lbs. steam pressure to flake form. This composition also possesses highly desirable detersive properties.

EXAMPLE III Using the procedure of Example I an improved detergent composition is prepared from the following components: 40% sodium propylene tetramer benzene sulfonate, 12.5% tri-sodium phosphate, 12.5% sodium silicate, 32% sodium sulfate, and 3% dodecyl benzene sulfonethanolamide. This composition exhibits excellent foam stability for 5, 10, and 15 minutes duration when subjected to the pour foam test set forth in U. S. Patent No. 2,315,983 to Ross and Miles.

EXAMPLE IV A liquid detergent is prepared containing about 50% monoethanolamine propylene tetramer benzene sulfonate salt, 15 dodecyl benzene sulfondiethanolamide, the remainder of the composition consisting essentially of water.

EXAMPLE V Another suitable liquid detergent composition is prepared by compounding 40% tri-ethanolamine salt of dodecyl benzene sulfonate, dodecyl benzene sulfonethanolamide, the remainder being a aqueous ethanol solution.

Other formulations productive of desired results are:

EXAMPLE IX Percent Sodium dodecylbenzene sulfonate 9 Sodium lauryl sulfate 10 Dodecyl benzene sulfondiethanolamide 4 Sodium carboxyrnethylcellulose 0.5 Sodium carbonate 1.5 Sodium sulfate 20 Sodium tri-polyphosphate 43 Tetrasodium pyrophosphate 12 EXAMPLE X Coconut fatty acid amides of taurine 25 Sodium sulfate 28 Sodium tri-polyphosphate 40 Dodecyl benzene sulfonethanolamide 7 The term consisting essentially of as used in the definition of the ingredients present in the composition claimed is intended to exclude the presence of other materials in such amounts as to interfere substantially with the properties and characteristics possessed by the composition set forth but to permit the presence of other materials in such amounts as not substantially to affect said properties and characteristics adversely.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications can be substituted therefore without departing from the principles and true spirit of the invention.

Having described the invention What is desired to be secured byLetters Patent is:

1. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide additive represented by the formula:

Z wherein R is a higher alkyl group, X is a mononuclear aromatic nucleus, Y is selected from the class consisting of hydroxyalkyl groups having up to 5 carbon atoms and polyalkyleneoxy groups, and Z is selected from the class consisting of hydrogen, lower alkyl groups having up to 5 carbon atoms and the groups specified for Y above, said polyalkyleneoxy groups having an average total of up to about 9 molecular quantities of alkylene oxide of 2 to 4 carbon atoms, the amount of said sulfonamide being less than the weight of said water-soluble anionic detergent and sufiicient to improve the soil removal power thereof. 7

2. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the Water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide additive represented by the formula:

2 wherein R is a higher alkyl group of 12 to 18 carbon atoms, X is a benzene nucleus, Y is selected from the class consisting of hydroxyalkyl groups having up to 5 carbon atoms and polyalkyleneoxy groups, and Z is selected from the class consisting of hydrogen, lower alkyl groups having up to 5 carbon atoms and the groups specified for Y above, said polyalkyleneoxy groups having an average total of up to about 9 molecular quantities of alkylene oxide of 2 to 4 carbon atoms, the amount of said sulfonamide being from about 1 to about 15% by weight of the detergent composition.

3. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting 9 of Watef-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide additive represented by the formula:

R-X-SO2NHY wherein R is a higher alkyl group, X is a mononuclear aromatic nucleus and Y is a hydroxyalkyl group of up to 5 carbon atoms, the amount of said sulfonamide being less than the weight of said water-soluble anionic detergent and sufficient to improve the soil removal power thereof.

4. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a higher alkyl benzene N-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble anionic detergent and suificient to improve the soil removal power thereof.

5. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and dodecyl benzene N-ethanol sulfonamide in an amount from about 1 to about 15% by weight of the detergent composition.

6. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a sulfonamide additive represented by the formula:

R-X-S O z wherein R is a higher alkyl group, X is a mononuclear aromatic nucleus, and Y and Z are both hydroxyalkyl groups having up to 5 carbon atoms, the amount of said sulfonamide being less than the weight of said watersoluble anionic detergent and sufiicient to improve the soil removal power thereof.

7. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a higher alkyl benzene N-di-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble anionic detergent and suflicient to improve the soil removal power thereof.

8. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and dodecyl benzene N-di ethanol sulfonamide in an amount from about 1 to about 15% by weight of the detergent composition.

9. A detergent composition consisting essentially of a water-soluble detergent selected from the class consisting of the water-soluble anionic organic sulfate and sulfonate detergents, and a higher alkyl benzene N-ethyleneoxy sulfonamide having an average total from about 1 to about 9 ethyleneoxy groups, the amount of said sulfonamide being less than the weight of said water-soluble anionic detergent and sufficient to improve the soil removal power thereof.

10. A detergent composition consisting essentially of a water-soluble higher alkyl aryl sulfonate detergent and a sulfonamide additive represented by the formula:

polyalkyleneoxy groups, and Z is selected from the class consisting of hydrogen, lower alkyl groups having up to 5 carbon atoms and the groups specified for Y above, saidpolyalkyleneoxy groups having an average totalof up to about 9 molecular quantities of alkylene oxide of 2 to 4 carbon atoms, the amount of said sulfonamide being less than the weight of said water-soluble sulfonate detergent and sufficient to improve the soil removal power thereof.

11. A detergent composition consisting essentially of a water-soluble higher alkyl mononuclear aryl sulfonate detergent and a sulfonamide additive represented by the formula R-XSO2NHY wherein R is a higher alkyl group, X is a mononuclear aromatic nucleus and Y is a hydroxyalkyl group of up to 5 carbon atoms, the amount of said sulfonamide being less than the weight of said water-soluble sulfonate detergent and suflicient to improve the soil removal power thereof.

12. A detergent composition consisting essentially of a water-soluble higher alkyl benzene sulfonate detergent and a higher alkyl benzene N-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble sulfonate detergent and sufiicient to improve the soil removal power thereof.

13. A detergent composition consisting essentially of a water-soluble higher alkyl benzene sulfonate detergent and dodecyl benzene N-ethanol sulfonamide in an amount from about 1 to about 15 by weight of the detergent composition.

14. A detergent composition consisting essentially of a water-soluble higher alkyl mononuclear aryl sulfonate detergent and a sulfonamide additive represented by the formula:

wherein R is a higher alkyl group, X is a mononuclear aromatic nucleus, and Y and Z are both hydroxyalkyl groups having up to 5 carbon atoms, the amount of said sulfonamide being less than the weight of said watersoluble sulfonate detergent and suflicient to improve the soil removal power thereof.

15. A detergent composition consisting essentially of a water-soluble higher alkyl benzene sulfonate detergent and a higher alkyl benzene N-di-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble sulfonate detergent and sufiicient to improve the soil removal power thereof.

16. A detergent composition consisting essentially of a water-soluble higher alkyl benzene sulfonate detergent and dodecyl benzene N-di-ethanol sulfonamide in an amount from about 1 to about 15% by weight of the detergent composition.

17. A detergent composition consisting essentially of a water-soluble higher alkyl sulfate detergent and a higher alkyl benzene N-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said watersoluble sulfate detergent and suflicient to improve the soil removal power thereof.

18. A detergent composition consisting essentially of a water-soluble higher alkyl sulfate detergent and a higher alkyl benzene N-di-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said watersoluble sulfate detergent and sufiicient to improve the soil removal power thereof.

19. A detergent composition consisting essentially of a water-soluble higher fatty acid monoglyceride monosulfate detergent and a higher alkyl benzene N-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble sulfate detergent and sufiicient to improve the soil removal power thereof. 20. A detergent composition consisting essentially of a water-soluble higher fatty acid monoglyceride mono- 5 sulfate detergent and a higher alkyl benzene N-di-ethanol sulfonamide having about 12 to 18 carbons in said higher alkyl group, the amount of said sulfonamide being less than the weight of said water-soluble sulfate detergent and sufiicient to improve the soil removal power thereof. 10

References Cited in the file of this patent UNITED STATES PATENTS Orthner May 28, 1935 Bren Feb. 23, 1937 Albrecht Sept. 21, 1937 Dietrich Apr. 23, 1940 Richardson Aug. 28, 1945 Games Aug. 18, 1953 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER-SOLUBLE DETERGENT SELECTED FROM THE CLASS CONSISTING OF THE WATER-SOLUBLE ANIONIC ORGANIC SULFATE AND SULFONATE DETERGENTS, AND A SULFONAMIDE ADDITIVE REPRESENTED BY THE FORMULA: 